It is important to understand the mechanism of oxidation in the initial stage on the free surface of liquid metals. Mittemeijer and co-workers recently developed a thermodynamic model to study the oxide overgrowth on a solid metal surface. Based on this model, we have developed a thermodynamic model to analyse the thermodynamic stability of oxide overgrowth on liquid metals. The thermodynamic model calculation revealed that the amorphous oxide phase is thermodynamically preferred up to 1.3 and 0.35 nm respectively, in the initial oxide overgrowth on liquid Al and Ga at the corresponding melting point. However, the amorphous phase is thermodynamically unstable in the initial oxide overgrowth on liquid Mg. The thermodynamic stability of amorphous phase in the Al and Ga oxide systems is attributed to lower sums of surface and interfacial energies for amorphous phases, compared to that of the corresponding crystalline phases.